Polymerizable and polymerized isocyanate compositions



Patented Aug. 12, 1952 t J I 2 6 i 1' e L v t J PGLYMERIZABLE AND POLYMERIZED ISQOCYANATE COMPOSITIONS v Edward'Li Kropa,'0ld Greenwich, and Arthur S. Nyquist; Cos Cob;-Gonn., assignors to American Cyanamid Company, New York, N. Y., a corpo- I ration of'Maine- I No' Drawin Application August 30, 1946, 'f' Serial No. 694,156

I 22 Claims (Cl.2608 0.3)

This invention relates'to new 'and useful commay be classed, either as divalent saturated alipositions of matter andmore particularly to poly merizable and polymerized jisocyanate compositions.

Still more particularly; the invention is con-' 4,alphaxylylene, Z-gamma-phenyIenebutyI; etc. cerned with polymerizable compositions 'compris- It is an object of the present invention to preing a mixture of (l) a primary isocyanate-repre pare new copolymers- Another object of the insented by the generalfo'rmula j vention is to prepare liquid compositions which are especially valuable in treating textile 'm'a- CHPCMMMTCHZTNCQ 10 terials, e. g., cotton, wool, rayon, etc., to impart where R represents aimember of the classconimproved properties thereto. Another object of sisting 'of hydrogen and" the methyl radical; A the inventionis toprepare coating, laminating, represents a member of the class consisting of and molding compositions and molded articles divalent saturated aliphatic'hydrocarbon radicals, utilizing new c opolymers For example, the divalent aromatic hydrocarbonradicals'divalent copolymer may be used as a binder for a filler saturated aliphatic-substituted aromatic'hydroor in pretreating, fillers, e. g; alpha-cellulose, c'arbon'radic'als'and' divalent aromatic=substituted wood, flour, et c., prior to incorporation in a molds aturated aliphatic hydrocarbon "radicalsgand n ing composition. Other objects will be apparent has a value which is "one .of the following: 0; 1, to those skilled in the artfas the descriptioneof the themethylene radical. attached to the isocyanate .inventionproceeds. h grouping being attached'directly; ,When'n is 1,-t0 It was suggested prior to our-invention that any carbon atom of the divalent-radical reprecopolymers of a l-alkenyl isocyanate, e. g., vinyl sented by A,,and (2) adifferentorganiccomisocyanate, with a vinyl or a vinylidene compound which is copolyrnerizable "with-the iso pound, specifically vinyl acetate, styrene and cyanate of (1') which contains a sing'le methyl methacrylate, might be prepared, I t;w as alsovsuggested thatsolutions ofsuchcopolymers "cra e e app e to fa rics in rd ..to.im a t Wate j 1, f repellency thereto.- However, to the; best o;f; ou r grouping and which is free-from'ahydrogen atom knowledge and-belief, it was not known; hereto or atoms reactive with the isocyanate-grouping, fore that iso cyanates of .t l f d the proportions o'f the said ingredients of 1) the general formulaCI-Iz zCR -j (An cl-l Q and (2) in the said'mix'ture being such" that the where R, A, and n have the meanings given-in resulting polymerization'product has an average thesecond paragraph or this specification would of at least two 'isocyanategroupings per-mol yield, upon polymerization with a compound andwiththe products of polymerization-of the which is copolymerizabletherewith, hi 1 said polymerizablecomposition. tains a single Y' f Illustrative examples of divalent radicals that e A 'in' the aforementioned general formula for the CH2=O\ pnmary lscyrnate may represent 5 ethylene grouping and which is free from. a-hydrogen atom propylene (trimethylene), butylene, isobutylene, 40 or atoms reacti. 1th th t l pentylene, isopentylene, hexylene, and other (e I h 1 W W elsocyan? divalent saturated aliphatic hydrocarbon radi- 0 fi Water @1 2 copqlymer composltions which, when appliedin solut1on .or cals, including divalent saturated cycloaliphatic dispersed State to woolengoods and the like ha 6 hydrocarbon radicals, e.' g.', cyclopentylene, cycloh baificulal; a peculiar, Git-y l hexylene, cycloheptylene, etc;; phenylene, na mg shrinka e" resistance thereto and et 1 tthylene, biphenylene; and other divalent aromatic m i' fi tw h' g' 'fi' h Q v. amount of treating hydrocarbon radicals; 2,4-tolylene, xylylene, agent a a a i-Sjrequira- For ethyl 2,5-phenylene, propyl 2,4,-phenylene, isov e p when a toluenesolution of a soluble copolymer propyl BA-phenyIe e, l-butyl w2i4'naphthylene of allylisocyanate 'a'ndethyl acrylatewas'applid and other ent sa d aliphatic-subsfito a fp eeejoi wee1en goods and the 'tteatea enes tuted aromatic hydrocarbo rad cal e was heated to evaporate the solvent and to inethylene, p yl py e, p nyl ut a solubilize the copolymer, the treated'jcibth eat thylethylene, naphthylisobutylene, and other after ,five' launderings showed a shrinkage'of-only divalent aromatic-substituted saturated aliphatic 3.3%: In marked contrast; untreated woolen hydrocarbon radicals; as-well' as radicals that cloth-when similarly laundered for thesame phatic-substituted aromatic or divalent aromaticsubstituted saturated aliphatic hydrocarbon radicals, e. g., 4,alpha'-tolylene, 3,beta-pheny1eneethyl number of times showed a shrinkage of 44.5%. It was quite unexpected and unpredictable that isocyanate copolymer compositions of the kind described in the second paragraph of this specification would impart such outstanding shrinkage resistance to an organic fabric, specifically a woolen fabric. Even more surprising was the fact that this shrinkage resistance was imparted to the woolen goods without in any way lessening its softness to the touch, and that these results were obtained by impregnating the woolen fabric with only about 8 to 9% by weight of copolymer, since with most treating materials about 14 to 16% by weight of treating agent, based on the dry weight of the woolen goods, is required in order to impart satisfactory shrinkage resistance thereto.

The improved results obtained with the copolymer compositions of our invention are believed to be due to the fact that the linear molecules of the copolymer, which in all cases contains an average of at least two isocyanate groupings per molecule and may contain an average of as many as, for example, 200 or more isocyanate groupings per molecule, react with the fiber molecules of the wool to form another cross-linked polymer. This new product consists of two linear materials which are interwoven, namely, molecules of the wool fiber joined with molecules of resin. The soft hand, that is, soft feeling to the touch, is believed to be due to flexible resin linkages between the wool molecules. Usually, when other materials are applied to wool in order to render it shrink-resistant, a harsh finish results due to the fibers of wool becoming drawn together. By using copolymers of the kind with which this invention is concerned in treating the wool, the rubber-like portion of the copolymer molecule, which portion is derived from the acrylic or other monomer copolymerized with the isocyanate, provides flexibility between the wool molecules with the result that the treated wool has a soft hand. 7

By employing isocyanate copolymer compositions of the kind hereinbefore described, it is possible to obtain better control of the shrinkage of, for example, wool than is possible by the use of conventional materials. Another advantage is that a lesser amount of treating material than generally is employed produces the desired results. For example, if it is desired to treat cotton or rayon in order to render it shrinkresistant, it'is common practice to use approximately 2- to 4% of a conventional resinous material to effect this result. However, if the cotton or rayon material also is to be madecreaseresistant, then ordinarily it requires about 8 to of a conventional resin in order to impart this property to the material. In the case of wool, as much as about 16% of conventional treating material may be required in order to provide satisfactory shrinkage and crease control of the woolen fabric.

By using our isocyanate copolymer composition, outstanding shrinkage control and also crease control can be effected with the same amount of treating agent with obvious advantages. Furthermore, the same isocyanate copolymer may be applied to textile materials made either of cotton, rayon or wool, or may be. applied to mixed fabric materials, for example, textiles made of rayon and cotton, rayon and wool, rayon and regenerated fibers (both cellulosic and protein) and the like. An additional advantage, as previously indicated, .is that a lesser amount of treating agent is required as compared with conventional materials.

It is believed that these improved results are due to the fact that the isocyanate copolymers with which our invention is concerned contain an isocyanate grouping which is attached to a primary carbon atom. The attachment to the primary carbon atom appears to serve a twofold function. First, it places the isocyanate grouping sterically off the main polymeric chain, putting it in a position more favorable for chemical reaction with any hydrogen-donor molecule; and secondly, the presence of an isocyanate grouping which is attached to a primary carbon atom renders such a grouping much more chemically reactive with hydrogen-donor materials.

The foregoing explanation is supported by other known facts. For instance, it is commonly known that a primary hydroxyl grouping reacts with a hydrogen-donor material many times faster than a hydroxyl grouping which is attached to a secondary carbon atom. Moreover, hydroxyl groups on tertiary carbon atoms are usually inactive under the same conditions. It also is generally known that almost any resinous material, when applied to a fabric, will impart some degree of finish to the fabric, but it is only in those cases where extensive and complete chemical reaction occurs between the resin and the fabric that one secures a satisfactory degree of both shrinkage and crease resistance. I

The isocyanates used in practicing our invention may be prepared, for example, by three general methods: the first involves the reactionof the corresponding alkenyl halide with a metallic isocyanate; the second involves the metathesis of the corresponding alkenyl urea and an isocyanate, which latter may be monoor polyfunctional; while the third involves the reaction of the corresponding amine with phosgene and the dehydrohalogenation of the corresponding acid chloride thereby obtained.

Since all of the amines used in the preparation of these isocyanates are attached to a primary carbon atom they may be produced by the catalytic reduction of a suitable derivative of the corresponding nitrile. Inasmuch as the reduction of the nitrile to the amine would destroy the final unsaturation, it is necessary to protect this grouping during the reduction. This may be. done, forexample, by the reduction of the corresponding carbinol derivative of the nitrile andsubsequent dehydration and reaction with phosgene. The resulting acid chloride is then dehydrohalogenated to yield the isocyanate.

Illustrative examples .of primary isocyanates that may be used in practicing the present invention and which are embraced by the general formula CH2:CR(A)nCH2-NCO, where R, A and n have the meanings hereinbefore given, are listed below:

Allyl isocyanate Gfl OH-OlEh-NC 0 Methallyl isocyanate v CHl=C-CHz-NO 0 3-butenyl isocyanate.

I QH2=CHCH2CH2NCO 3-methyl 3butenyl isocyanate CH=CCH:-CHz-NCO CH3 v d-pentenyl isocyanates om=onc,m crcl ioo by mixing the primary isocyanate with a difierent organic compound'of the kind hereinbeiore described, numerous examples of which have previously been given. Examples ofpreierred classes of such compoundsare the N,N-dialkyl acrylamides, the acrylic esters of saturated aliphatic monohydric alcohols and the vinyl esters of saturated aliphatic monocarbox-ylic acids. The copolymerizable materials are mixed in proportions such .that the resulting copolymer has an average of at least two isocyanate groupings per molecule. Such a product is obtained when the mixture contains, by weight, for instance, from about 3 to of the primary isocyanate, e. g., allyl isocyanate, methallyl isocyanate, etc., and from about 97 to 70% of the other copolymerizable monomer, e. g., N,N-di butyl acrylamide, ethyl acrylate, vinyl acetate, etc.

' Themixed ingredients are copolymerizedunder anhydrous conditions. Copolymeriz'ation may be effected, for example, under the influence'of ultraviolet light, with or without heat and with or without a catalyst such, for instance, as benz'oyl peroxide or other organic peroxide which is free from a hydrogen atom or atoms that would react with th isocyanate grouping. If desired, themixed ingredients may be copolymerized'in solution state, for instance, in solution in anin ert organic solvent, e. g., toluene, benzene, xylene, dioxane, ethers (e. g., dibutyl ether), esters (e. g., butylacetate), chlorobenzene, ethylene dichloride, ketones' (e. g., methyl ethyl ketonel, etc. The temperature of copolymerization may be varied as desired or as conditions may require, but ordinarily will be within the range of from about 20 to about 150 'C.When copolymerization is effected in the absence of a solvent; When the mixed ingredients are copolymerized in solution state,'then copolymerization generally is effected at theboiling temperature of the. solution. In all cases, the temperature of 'copolymerization'is below the decompositiontemperature of the mono-' meric materials.

In copolymerizing the primary isocyanate with the other copolymerizable monomer we prefer to use heat and a catalyst which is free from hydrogen or other groups-reactive with the isocyanate grouping, e. g., benzoyl peroxide, di-(tertiary-butyl) peroxide, acetyl peroxide, etc., sincethereby We are better able to obtain soluble c'opolymers. When such a soluble copolymer is exposed to light, insolubilization occurs' This reaction appears to take place through'the direct polymerization of the isocyanate grouping. It is possible to effect insolubilization by exposing the copolymer to the action of ultraviolet light or by long exposure to diffused daylight. Whenthe 'copolymerization is conducted under conditions involving ultravioletlightand a peroxide, both soluble and partially soluble copolymers maybe produced. By proper selection of the polymerization conditions it is possible to obtain, at will, soluble or insoluble materials. In order to preserve soluble copolymers which are suitable for reaction with hydrogen-donor materials it; is preferableto store such copolymers or solutions ofthe same in the absence'of light. On the-other hand, it is possible to obtain an insolublefilm of copolymer by exposing a film of the soluble co-' polymer to the action of ultraviolet light or, for a longer period, to the action of diffused light.

Aspointed out hereinbefore, lt'iS advisable during the copolymerization-to" avoid the use of any compounds which are capable of .reactmgwith the ,isocyanate grouping, .e g., alcohols, acids,

water, etc. Inthe 'case-orthe high molecular weight copolymers it has been found that after dissolving them in an organic liquid which is insoluble in water, it is possible to emulsify the organic solution of the copolyineric isocyanate. The presence of the organicli'quid'appears to act as a barrier to "prevent water from coming into contact with the copolymeric isocyanate. In order further to impede the transfer of liquid water and water vapor, one can introduce into the initial solution a small amount of material which is known to impede the transfer of water vapor, e. g., for example, polyethylene, crystalline products such as pa'raiiin, mi'cr'ocrystalline waxes,

In order that those skilled in the art better may understand how the present invention may be carried into effect, thefollowing examples are given by way of illustration and not by way of limitation. All parts are by weight.

Example '1 Parts Ethyl acrylate j 45.0 Allyl isocyanate 5.0 Benzoyl peroxide 0.2

were mixed together and placed in a quartz flask inclined and fitted with a 3-Way adapter. A reflux condenser was attached to the vertical joint of the adapter and a gas delivery tube was attached to the adapter joint opposite from the flask. A slow stream of dry carbon dioxide was passed through the flask during the course of the reaction. The flask was irradiated from below, thus directly on the reaction mass, with a small laboratory size Mico ultra violet lamp, the lamp being mounted about 1 /2 inches from the flask.

Irradiation of the catalyzed mixture of monomers was continued for 162 hours. At the end of this time, the ethyl acrylate' and allyl isocyanate had copolymerized to a clear mass which, although soft, had little tendency to fiow.

When the polymeric mass was dissolved in dry toluene, most of it went into solution. However, part of the copolymer; although it swelled highly, did not dissolve. Apparently, a certain amount of cross-linking, occurred during the polymerization reaction. When a small portion of the toluene solution was treated with a few drops of ethylene diamine, gelation occurred almost immediately. Similarly, when a small portion of the toluene solution was treated with p-phenylene diamine, although no reaction occurred immediately, warming on the steam bath for several minutes was sufficient to cause gelation. This illustrates the high degree of reactivity of the copolymer. I

Twelve parts of the. above solution which contained about 30% by weight, of copolymer, was diluted with 68 parts of dry toluene to give parts of a solution containing-about 5%, by weight, of copolymer. Two pieces of cotton poplin were then treated directly with this solution. The pieces of fabric were immersedin the solution for about 10 to 15 seconds, squeezed out and allowed to air-dry until all the solvent had evaporated. One piece of the treated cloth was then heated in an over at 120 C. fore minutes. The second piece of treated cloth was heated in an oven at 120 C. for 7 minutes. A third piece of the poplin, which had beenpre-dried by heating in the oven at 'C;'for about 40 minutes, was also treated with the copolymer solution and,

treatment at repellency, all three pieces of treated cloth were definitely superior to the untreated cloth.

A piece of woolen goods was treated with-a toluene solution containing about 10% by weight of the copolymer of this example. The wool sample (9" x 23" in size) was immersed in the solution, and passed through squeeze rolls to give 80-90% wet pick-up (8-9% solids). The sample was framed, air-dried for a short period, and then heated for 9 minutes at 290 F. After cooling to room temperature, the sample was removed from the frame, allowed to remain undisturbed for about 16 hours and was then measured prior to laundering. The methodof laundering was a modification of the standard method of the A. A. T. C. C., and involved heating for 20 to 30 minutes at 240 F. while drying after each washing. After a cycle of washing minutes in soap solution) and drying operations, and a final washing of 1 hour in the soap solution, the dried treated cloth showed a shrinkage of only 3.9%. In marked contrast, untreated woolen cloth when similarly laundered for the same number of times showed a shrinkage of 44.5%. After Washing and drying cycles, the shrinkage was only 4.2%. The laundered cloth had a soft hand.

Cotton goods treated with the above 10% copolymer. solution was found to have 100% retention to soaping and dry cleaning.

The copolymer of this example imparts a good degree of crease resistance to fabric materials, e. g., rayon. Thus, when a sample of rayon was treatedwith a 10% toluene solution of the copolymer, the treated rayon showed a crease-resistance value of 6.7,whereas the crease-resistance value of the untreated rayon was 5.1 (Tootal, Broadhurst and Lee standard method of determining crease resistance). Similar results are obtained when methallyl isocyanate is substituted for allyl isocyanate in the above'formula and the resulting copolymer is used as hereinbefore described.

Example 2 Parts Butyl acrylate 90.0 Allyl isocyanate 10.0 Benzoyl peroxide 0.4 Toluene (dry) -1 33.0

The toluene was placed in a flask and heated underreflux while maintaining a bath temperature of 130 to 135 C. The mixture of the other ingredients was added dropwise over a period of a small portion of this solution was treated with 2 to 3 drops of ethylene diamine, gelation occurred almost immediately upon stirring the mixture. One hundred and eighty-two (182) parts of the 38.5% solution was thinned with additional toluene to yield a solution containing about 10% by weight of copolymer. This solution was used in treating wool as described under Example 1. After a cycle of 5 washing and drying operations, and a final washing of 1 hour in the soap solution, the dried, treated piece of wool showed a shrinkageof 5.8%. After 15 washing anddrying cycles, the shrinkage was 6.7%. The treated cloth had asoft hand. 5 7 I Example 3 v Parts Butyl acrylate 90.0 Allyl isocyanate 10.0 Benzoyl peroxide 0.4

were mixed together and subjected to ultraviolet light while the mixture was exposed to an atmosphere of carbon dioxide. After exposure for about 2 hours, an increase in the viscosity of the solution was noted. After 18 hours exposurethe mixture was clear, very viscous but still flowed. After a total of hours exposure, during which time the flask occasionally was rotated so that a new surface was exposed to the light, a clear polymeric mass was obtained which had no, appreciable flow when the flask was tipped. One hundred parts of dry toluene was mixed with the copolymer produced as above described and allowed to stand for about 3 days. Some of the copolymer dissolved in the toluene, but the greater part of it was in a highly swollen but insoluble gel state. This was apparently due to cross-linking brought about by the allyl isocyanate during the polymerization. The soluble portion of the material was decanted and the gel that remained was then twice extracted with additional toluene. This solution may be used in treating cotton, wool, rayon, silk, etc., to improve their properties. I

Four pieces of muslin were impregnated 3 times with a toluene solution containing about 15% by weight of the above-described butyl acrylate-allyl isocyanate copolymer, the pieces being air-dried after each impregnation. The impregated sheets were superimposed, and laminated by heating between steel plates for 8 minutes at to C. under a pressure of approximately 50 pounds per square inch. A flexible, well-bonded laminated sheet was obtained. Cross-linking of the copolymer occurred during curing.

Example 4 Same formula as in the preceding example. Ultraviolet radiation was applied to the'mixed ingredients in a quartz flask under anhydrous conditions using a small Mico ultraviolet'lamp placed about 1 inches from the flask. After 75 minutes treatment, a slight but definite increase in viscosity was noted. After about 31 hours total irradiation, 100 parts of dry toluene was addedto the resulting copolymer, but the solid copolymer did not completely dissolve in the toluene even after standing for about 6 days. An additional 100 parts of dry toluene was now added anddissolution of the copolymer therein was hastened by shaking the container. An appreciable amount of highly swollen, gelled copolymer was present in the mass, but the amount thereof was considerably less than that resulting from the preceding example. The solution was'strained to remove gel particles, and additional dry toluene was added to yield a solution containing about 20.8% by weight of copolymer. Three hundred parts of the resulting solution was transferred to a one-liter flask and part of the solyent was distilled off at reduced pressure to remove any unreacted monomers. The solution was then diluted with additionaldry toluene toform a'solution containing about by weight of copolymer. This solution was used in treatingwool as-described under Example 1. After a cycle of- 5 washingand drying operations, and a final washing of 1 hour in the soap solution, the dried, treated piece of wool showed a shrinkage of 4.2%.

After washing and drying cycles, the shrinkage was 5.3%. The treated cloth had a soft feeling to the touch. 7

" Example 5 Parts Ethyl acrylate 95.0 Allyl isocyanate 5.0 Benzoyl peroxide 0.4

Toluene (dry-)- 67.0

sure'in order to remove any unreacted monomers; Two hundred and forty parts of the resuiting solution was diluted with 460 parts of dry toluene to yield a solution'containing about 10% by weight of copolymer. This solution was used in treating wool as described under Example 1.

The shrinkage after a cycle of 5 washing and drying operations, and a final washing of 1 hour in the soap solution followed by drying, was 5.8%.

After 15 washing and drying cycles, the shrinkage, was 7.2%. The treated wool had a soft hand.

Example 6 Parts Ethyl acrylate 135.0 'Allyl isocyanaten 15.0 is Benzoyl peroxide; 0.6 Essentially the same procedure was followed as described under Example l-with the exception that the ultraviolet lamp was mounted about 1 inch from the flask. After 24 hours irradiation,

a clear, firm mass of copolymer was obtained. 1

One hundred parts of dry toluene was added to the copolymer composition, and after standing for about 6 days another 150 parts of toluene was added'thereto. The solution was strained after standing for another 6 days in order to remove undissolved gel particles. The strained solution contained about 32% by weight of copolymer. One hundred parts of this solution was diluted with dry toluene to form a solution containing about'20% by weight of copolymer. This solution was emulsified by adding it slowly to an equal amount of water containing about 1% by weight of thesodium salt of the sulfate of a mixture of lauryl and myristyl alcohols, while violently agitating the mixture. This emulsion is later referred to herein as sample A. Another portion of the copolymer solution was diluted with an additional amount of toluene to yield a solution containing about 10% by weight of copolymer. This solution is later referred to herein as sample B;

Samples Aand B were used in treating an organic fabric'material, specifically wool, asdescribed under Example 1. After a cycle of 5 washing and drying operations, and a final washing of 1 hour in the soap solution,-the dried piece of wool which had been treated with sample A showed a shrinkage of 4.4%, while the wool which had been treated with sample B showed a shrinkage of 2.8%. After 15 washing and drying cycles, the shrinkage ofthe wool treated with sample'A was 8.0% and that which hadbeen treated with sample 3,42%. In both cases the treated woolen fabric had a soft hand.

Example 7 1 Parts Acrylonitrile 18.0 Allyl isocyanate 2.0 Benzoyl peroxide 0.08

The acrylonitrile and allyl isocyanate were mixed and added to a glass tube to which the benzoyl peroxide previously had been added. The mixture was blanketed with carbon dioxide, and the container was stoppered until ready for sealing. Thereafter it was cooled in dry ice and sealed while evacuating with a water pump,1iushing out the container 4 or 5 times with carbon dioxide before sealing. The sealed container was allowed to stand for about 16,hours at room temperature, after which it was subjected to irradiation with ultraviolet light, using a Cooper- I-lewitt lamp placed about 15 inches from the container. After about 5 minutes irradiation, the solution started to become cloudy, apparently due to precipitation of the copolymer. The solution soon become opaque due to copolymer formation and had set to what appeared to be a solid mass before 8 hours had elapsed. After a total of 24 hours exposure, irradiation was discontinued.

When the sealed glass tube was opened, the opaque, slightly discolored mass was found to consist of a shell of transparent polymerized material within which the bulk of the product was contained in an opaque, white form. v

The copolymer composition of this example is suitable for use in preparing heat-resistant moldingcompounds which are capable of further cure.

Example 8 g Parts N-butyl acrylamide 18.0 Allyl isocyanate 2.0 Benzoyl peroxide; 0.08

The N-butyl acrylamide and allyl isocyanate were mixed together and added to a Pyrex glass vessel to which the catalyst previously had been added. The container was then sealed as described under Example '7. Although the catalyst dissolved only partly in the mixture of monomers, the mixture polymerised rapidly upon standing at room temperature. After about 96 hours the mixture, had partly solidified. After standing for about 24 days the copolymer was obtained in the form of a clear, solid mass which swelled but did not dissolve in dioxane, This copolymer may be used, for example, in the production of molded articles. Since N-butyl acrylamide is a compound containing a hydrogen atom capable of reacting with the isocyanate grouping of the allyl isocyanate, this example illustrates the results that are obtainedwhen such a material is copolymerized with a primary isocyanate of the kind with which this invention is concerned, specifically allyl isocyanate.

When N,N-dibutyl aorylamide is substituted for N-butyl acrylamide in the above formula, a copolymer is obtained' which is soluble in various inert liquids, e. g, toluene, etc.

Such soluble co- 113 polymers are suitable for-useintreating organic fabri'c. materials, e.:g.,, cotton, wool,--rayon, silk, -etc., -to impart improved properties. therefore.

i p 'e Y Paris '*Y ,inylfacetate 18.0 "Allyliisocyanatm '2-.0 'Benzoyl peroxide :08

jI-he same procedure was followedas described under Example 7. After 16 days" irradiation, a viscous, slightly discolored mass was obtained. After distilling oft theunreacted monomers, a clearcopolymeroi vinyl acetate and allyl'.isocy- .anate'. resulted.) .This copolyme'r'was' moderately hard at'room temperature. V

f.-.' A small portion of they polymer was dissolved .in dioxane and the resu'ltingsolutioni was treated with'a few drops ofethylene diamine. The mass gelled, showingthe high degree of reactivity of .the copolymer i i The copolymer'of this examplemay be used, for e mple, in thejpreparation of coatingcompositior'i's, as' 'a modifirof other resinousmaterials, or aloneorinicombination with other resins it may be',.emplo'.yed in the, production of cast or 'mplded articles.' l

were mixedtogetheriina quartz flask and exposed to;ultravioletlightlunder the; same: conditionsas described under Example 1. After 65 hours-the flask was rotated partly to expose a'newjsurface to vthe light. Exposure was-continued'for a total of 161 hours, the ethyl acrylate and the allyl isocyanateihaving copolymerizedat the end of this time .to a clear, soft, sticky mass which had no appreciablefiow.

move the gel particles, and the gel portion was then, extracted with an additional 25 parts of toluene. One hundred and sixteen'parts of solution containing 35 parts (approximately 30.1% by weight) of copolymer was obtained.

i When a small portion of the above solution was treated with ethylene diamine, gelation'occurred almost instantaneously; Similarly, when a small portion of the solution was treated with 2,2-dimethyl propanediol, although no reaction occurred immediately, heating in an oven at 100 C. for to minutes produced an insoluble, cross'-1inked,copolymer. I f: Woolen goods were treated with 22.10% solution of'the'jcopol'ymer' as described under Example 1. shrinkage after a cycle of 5.washing and jdryingloperations and a final washingof 1 hour followed by drying was 4.2%. The treated wool hada soft hand. Itwill be understood, of course, by those skilled in the art that our invention is not limited to the use of the specific ingredients named in the above illustrative examples nor to the particular proportions there shown. Thus, instead of allyl isocyanate wemay use, for instance, methallyl in general the isocyanate or minor proportion and material a greater or major isocyanate, ,.3-butenyl isocyanate, p-vinylbenzyl isocyanate or any other primary isocyanate or mixture thereof embraced by the general formula"CHz:CR(A)nCH2-.NCO where R, A and n havethe meanings. given in the second paragraph of this specification, numerous examples of which isocyanates were hereinbefore given. i i

Likewise, monomeric materials other r'than those specified in the examples maybe copolymerized with the primary isocyanateJ For example, we may use methyl acrylate, .propyl acrylate, hexyl' acrylate, methyl methacrylate, ethyl methacrylate, allyl acetate, methacrylonitrile or any other compound which: is copolymerizable with the isocyanate, which contains a single CHFO grouping and which is free from a hydrogen atom or atoms reactive with the isocyanate grouping, numerous examples of which compounds previously have been given. If desired, mixtures of monomers may be copolymerized with a single isocyanate or with a plurality of isocyanates.

Catalysts other than benzoyl peroxide also maybe employed, but if a catalyst is used it is desirable to use one which contains no hydrogen atom or atoms that will react with the isocyanate grouping. Examples of catalysts that may be employed are inorganic peroxides such, for example, as barium peroxide, etc.; dialkyl peroxides, e. g., lauryl peroxide, stearyl peroxide, di- (tertiary-butyl) peroxide, etc; symmetrical diacyl peroxides, e. g., acetyl peroxide, lauroyl peroxide, stearoyl peroxide, etc.; unsymmetrical or mixed diacyl peroxides, e. g., acetyl ben 'zo' yl peroxide, etc. Any suitable amount of catalyst may be used, but in general the catalyst concentration will be Within the range of about0l05 to 2 or 3% by weight of the mixed copolymer-'- 'izable materials.

The proportions of the ."copolynfi'erizable ingredients may be varied over a wide range, but in all cases the proportions are such that the resulting polymerization product has an average of at least two isocyanate groupings per molecule. Particularly useful copolymer compositions are obtained when the mixture of c'opolymerizable materials contains, by weight, from about 3 to 30% of the primary isocyanate and from about 97 to 70% of the other co polymerizable monomer. In producing soluble copolymers for use in treating wool and other textile materials, we prefer to use a mixture of, by weight, about 5 to 15% of the primary isocyanate and about 95 to of the other copolymerizable monomer. When the copolymer is used in such applications no particular advantage ordinarily accrues when the isocyanate is used in an amount much above about 15%, by weight, of the mixed ingredients. cote results have been "obtained with copolymers produced from a mixture or, by weight, "about 10% of the primary isocyanate and about of the other copolymerizable monomer.

plications it may be desirable to cyanate 'in an amount 30%, by Weight,of'the use the isosubstantially exceeding mixed ingredients, but will "constitute alesser the-"other monomeric proportion, by weight, of'the mixed copolymerizablematerials. The copolymer compositions of this invention have a wide variety of commercial applications For some ap- -the purpose of anchoring dyes in fabrics.

due to the fact that they will react with any compound or material containing an active hydrogen atom. In addition to their use in treating cotton, rayon, silk, wool, and other textile materials, they also may be employed for treating paper, leather, resin-coated surfaces, etc. They also-may be used in treating dyes prior to dyeing a fabric material or they may be employed to finish dyed fabrics: Because of the reactive nature of "these copolymers they also have application in anchoring fire-proofing and rainproofing agents on fabric and other materials. In a similar manner, they may be employed for In coating compositions the isocyanate copolymers of this invention may be used directly to secure cured films, the water vapor present in the air ordinarily being sufdcient to accelerate crosslinking.

The hardenable or potentially hardenable copolymers of this invention may be used alone or with fillers, dyes, pigments, opacifiers, etc., in a wide variety or casting, molding and laminating applications, as adhesives, impregnants, and surface-coating materials and for numerous other purposes. Thus they may be employed, for instance, in protectively coating surfaces of metal, Wood, synthetic resins, etc., or as a finish coating over painted surfaces.

These new copolymers may be modified by the addition of other reactive or non-reactive materials, or they themselves may be used as modifiers-of other substances Which are reactive or non-reactive with the copolymer. Illustrative examples of materials with which the reactive copolymers of this invention may be combined are compounds or substances containing one or more -OH groups, for instance: glycol, glycerine and other polyhydric alcohols; fatty oils or the kind exemplified by castor oil; diglycerides; alkyd resins containing -Ol-I groups; urea-formaldehyde condensation products, e. g., monoand dimethylol ureas and their partial condensation products; acetylene urea; melamine-formaldehyde condensation products, e. g., mono, di-, tri-, tetra-, pentaand hexa-methylol melamines and their partial condensation products; phenolformaldehyde condensation products, e. g., saligenin and the more highly condensed phenol alcohols; polyvinyl phenols; sugars; starches; polyvinyl alcohol and partially esterified and etherified polyvinyl alcohols; polyallyl and polymethallyl alcohols and partially esterified and etherfied polyallyl and 'polymethallyl alcohols; cellulose and cellulose derivatives containing free hydroxyl groups, e. g., partially esterifled cellulose, partially etherified cellulose, eta; partially or wholly methylolated acrylamides; water- ,soluble natural gums, e. g., agar agar, tragacanth,

pectin, etc.; silicols and their partial condensationproducts, e. g., mono-, diand tri-methyl silicols and mixtures thereof, mono-, diand triphenyl silicols and mixtures thereof, mixtures of any or. all of the aforementioned methyl and phenyl silicols, and partial condensation products of the aforementioned silicols and mixtures thereof.

Our new copolymers also may be combined with nitrogen-containing materials, e. g., ethylene imine, ethylene diamine, diethylene triamine, gelatin, chitin, monoamino and polyamino com pounds such, for instance, as wool, silk, zein, casein, regenerated fibers from soyabean, casein, collagen, etc., to yield new and useful materials 9.1 articles of manufacture.

16 The copolymers of this invention are especially valuable for use in the preparation of laminated and molded articles. Thus, they may be employed in treating sheet materials, e. g., paper, fabric materials of cotton, linen, asbestos, etc.,

which, with or without subsequent treatment with other resinous materials, e. g., melamine -aldehyde resins, urea-aldehyde resins, alkydresins.

etc., are thereafter dried, superimposed and laminated under heat and pressure to yield laminated articles wherein the copolymer has become an integral part of the sheet material. They also may be used advantageously in bonding together wood flour, alpha-cellulose and other finely divided fillers to form-molded articles of manufacture. In the case of those fillers that contain a hydrogen atom or atoms reactive with the isocyanate grouping, the copolymer reacts therewith to yield a product inwhich the copolymer is chemically bound therein. Finely divided fillers also may be pretreatedwith these new copolymers prior to incorporation in conventional molding compositions, e. g.,' phenolformaldehyde, urea-formaldehyde, melamineformaldehyde, etc., molding compositions. Or. the filler combined with phenol-formaldehyde, urea-formaldehyde or other synthetic resin may be treated with these new copolymers in the preparation of the molding composition.

The process of treating organic textile, hydrogen-donor materials with the reactive polymerization products of this invention and the products of such treatment are claimed in our copending application Serial No. 694,157, filed concurrently herewith, now Patent No. 2,537,064, dated January 9, 1951.

What We claim as new and desire to secure by Letters Patent of the United Statesis:

1. A polymerizable composition comprising a mixture of, by weight, a minor proportion of (l) a primary isocyanate represented by the general formula CH2=CR'(A)nCH2-NCO where R represents a member of the class consisting of hydrogen and the methyl radical, A represents a member of the class consisting of divalent saturated aliphatic hydrocarbon radicals, divalent aromatic hydrocarbon radicals, divalent saturated aliphatic-substituted aromatic hydrocarbon radicals and divalent aromatic-substituted saturated aliphatic hydrocarbon radicals, and n represents a value selected from the class consisting of 0 and 1, the methylene radical attached to the isocyanate grouping being attached directly, when n is 1, to any carbon atom of the divalent radical represented by A, and a major proportion of (2) a different organic compound which is copolymerizable with the isocyanate of (l), which contains a single CH:=C/

grouping, and which is free from a hydrogen atom reactive with the isocyanate grouping, the aforementioned proportions of the said ingredientsof (1) and (2) in the said mixture being such that the resulting polymerization product has an average of at least two isocyanate groupings per molecule.

2. A composition comprising the product of polymerization of a polymerizable mixture including, by weight, a minor proportion of ('1) a primary isocyanate represented by the general formula CHz:CR(A)nCH2NCO where R represents a member of the class consisting of hydrogen and the methyl radical, A represents a mem- Gin-o grouping, and which is free from a hydrogen atom reactive with the isocyanate grouping, the aforementioned proportions of the said ingredients of (l) and (2) in the said mixture being such that the said polymerization product has an average of at least two isocyanate groupings per molecule.

3. A copolymer as in claim 2 wherein the isocyanate of (1) is allyl isocyanate.

4. A copolymer which is soluble in inert organic liquids, said copolymer being the product of polymerization of a mixture containing, by

weight, (1) from about 3 to 30% of a primary isocyanate represented by the general formula CH2= CRF(A) nCH2NCO' where R represents a member of the class consisting of hydrogen and the methyl radical, A represents a member of the class consisting of divalent saturated aliphatic hydrocarbon radicals, divalent aromatic hydrocarbon radicals, divalent saturated aliphatic-substituted aromatic hydrocarbon radicals and divalent aromatic-substituted saturated aliphatic hydrocarbon radicals, and n represents a value selected from the class consisting and 1,

, the methylene radical attached to the isocyanate grouping being attached directly, when n is l, to any carbon atom of the divalent radical represented by A, and (2) from about-97 to 70% of an acrylamide containing a single grouping and which is free from a hydrogen atom where R represents a member of the class consisting of hydrogen and the methylradical, A

represents a member of the class consisting of divalent saturatedaliphatichydrocarbon radicals, divalent aromatic hydrocarbon radicals, divalent saturated aliphatic substituted aromatic hydrocarbon radicals and divalent aromatic-substituted saturated aliphatic hydrocarbon radicals, and n represents a value selected from the class consisting of 0 and 1, the methylene radical attached to the isocyanate grouping being attached directly, when n is 1, to any carbon atom of the divalent radical represented by A, and (2) from about 97 to ing a single 70% of an acrylicester containcHFd grouping, and which-is'freefrom a hydrogen atom reactive with the isocyanate grouping, said ingredients of (1) and.(2) being copolymerizable.

'7. A copolymer as in claim 6. wherein the acrylic ester of (2) is ethylacrylate.

8. A copolymer which, is soluble in inert organic liquids, said copolymer being the :product of polymerization of a mixture containing, by weight,

(1) from about 3 to ,ofa primary isocyanate represented by the general formula where R represents a member of the classconsisting of hydrogen and the methyl radical, A represents a member of the class consisting of divalent saturated aliphatic hydrocarbonradicals, divalent aromatic. hydrocarbon radicals, divalent saturated aliphatic-substituted aromatic hydrocarbon radicals and divalent aromatic-substituted saturated aliphatic hydrocarbon radicals, and n represents a-value selected from the class consisting of 0 and 1, the methylene radi- --cal attached to the isocyanategrouping being attached directly, when n is 1,-- t o any carbon atomof the divalent radical represented by A, and (2 from about 97 to 70% of avinyl ester containing a single grouping, andwhich is, free-from a hydrogen CH2=CR (A) 11-cH2 Nco where R represents a member of the class consisting of hydrogen and the methyl radical, A represents a member of the class-consisting vof divalent saturated aliphatic hydrocarbon radicals, divalent aromatic hydrocarbon radicals, divalent saturated aliphatic-substituted aromatic hydrocarbon radicalsand divalent aromatic-substituted saturated aliphatic hydrocarbon radicals, and n representsa value selected from the class consistingv of 0; and 1, themethylene radical attached to theisocyanategrouping being attached directIyQWhen n is ,1, to any carbon atom of the divalent radical represented by A, and (b) from about 97 to 70% of an acrylic compound containing a single oHi=o grouping and which is -free-from :a hydrogen atom reactive with the isocyanate' grouping, said ingredients of (a) and (blbeing copolymeriz'able,

and (2) a liquid which will'dissolve said copolymer and which is inert'thereto. Y

11. A toluene-soluble copolymer of, by weight,

a minor proportion of. allyl-uisocyanate and a I a minor: proportion of .allyl isocyanate and: a *major proportion of vinyl acetate, said copolymer having an averageof. at least two isocyanate groupings per moleoule.

'14. A'compos'ition comprising the product of 'polymerization of a'mixture' of, by weight, from about 3 to 30% ofallylisocyanate and from 97 I to 70%oil' an N-,N dialkyl acrylamide.

15. A compo'siti'oncomprising the product of polymerization of: a mixture of, by weight, from about 3 to 30% of allyl isocyanate and from about 9'7 to 70% 'of an 'acrylicester of a saturated aliphatic monohydricalcohol.

16. A composition'comprising the product of polymerizationoi a mixture of, by Weight, from about 3 to-30 of 'allylisocyanate and from about 97 to 70% 'of a'vinyl esteroi a saturated aliphatic monocarboxylic acid.

1'7. The method of preparing new synthetic compositions which comprises polymerizing under anhydrous conditions a mixture containing, by weight, a minor proportion of (1) a primary isocyanate represented by the general formula 'Cl-I2=CR-'(A) n'CH2-NCO where R represents 7 a member of the class consisting of hydrogen and the methyl radical, A represents a member of the class consisting of divalent saturated aliphatic hydrocarbon radicals, divalent aromatic hydrocarbon radicals, .divalent saturated aliphaticsubstituted aromatic hydrocarbon radicals and divalent aromatic-substituted saturated aliphatic hydrocarbon radicals, and n representsa value selected fromiithe class consisting of 0 and 1, the methylene radical attached to the isocyanate grouping being attached'directly, when n is 1, to any carbon atom ofthedivalent radical represented. by A", and. a major proportion of (2) a different organicwompound which is copolymerizable Withtheisocyanate of (1), which contains a single grouping'andwhichis free-from a hydrogen atom reactive withthe'isocyanate grouping, the

aforementioned proportions of the said ingredients of (1) .and"(2):-in the said mixture being such thatthe resultingpolymerization product has an average ofat'leastitwo isocyanate groupings per molecule. I. Y

$18; A substancejcomprising the'product of reactionof (1) a" product. of polymerization of a polymerizablefmixtureincluding, by weight, a

1minor proportionpf (a) a; primary isocyanate 'represented'byithegeneral'formula hydrocarboniradicals anddivale'nt aromatic-substituted saturated aliphatic :hydrocarbonradicals, and n represents avalueselected from the class consisting'of 0.and 1,: themethylene radical attached. to. .the;:isocyanate: grouping being atgtached directly, whenlnis 1,-to any carbon atom of the divalent radical represented by A, and a major proportionof (b) a different organic compound which is copolymerizable with theisocyanate' of (a) ,Which contains a single grouping, and which is free from a hydrogen atom reactive with the isocyanate grouping, the

aforementioned proportions of the said ingredimerization product has an average of at least two isocyanate groupings per molecule,and (2) a compound containing a hydrogen atom which is reactive with the isocyanate groupings present in the polymerization product of (1).

19. A composition comprising the product of polymerization of a polymerizable mixture including allyl isocyanate and ethyl acrylate, the allyl isocyanate constituting, by weight, from about 3% to about 30% and the ethylv acrylate constituting from about 97% to about of the said polymerizable mixture.

20. A composition containing, as an essential reactive ingredient, a reactive copolymer of about to by Weight. of ethyl acrylate and about 5 to 10% by weight of allyl isocyanate.

21.. The method .of producing a composition comprising a reactive copolymer of ethyl acrylate and allyl isocyanate which comprises preparing a mixture of, by weight, 45 parts of ethyl acrylate, 5 parts of allyl isocyanate and 0.2 part of benzoyl peroxide, copolymerizing the ethyl acrylate and allyl isocyanate components of the said mixture under the influence of ultraviolet light while admixed with the said benzoyl peroxide and while passing a slow stream of dry carbon dioxide through the reaction mass during the course of the copolymerization reaction, and continuing the oopolymerization reaction under the aforementioned conditions until there has been obtained a reactive copolymer characterized by the fact that most of it is soluble in dry toluene.

22. The method of producing a toluene solution of a reactive copolymer of ethyl acrylate and allyl isocyanate which comprises preparing a mixture of, by weight, 95 parts of ethyl acrylate, 5 parts of allyl isocyanate and 0.4 part of benzoyl peroxide, adding said mixture slowly to a mass of dry toluene, heating the resulting mixture under reflux for a period of the order of 4 hours after. the addition of all of the said mixture to the said toluene, thereafter adding afurther amount of dry toluene to the mass, and distilling oif aportionof the added toluene underreduced pressure concurrently with the removalof any unreactedmonomers.

EDWARD L; KRO-PA.

ARTHUR S. NYQUIST.

REFERENCES CITED The following. references, are .of recordjn-the file of this patent:

I UNITED STATES PATENTS Number Name Date 2,326,287 Cofiman 'Aug. 10, 1943 2,335,582 Coffman Nov;'30,'.1943

OTHER REFERENCES Beilstein, Organische Chemie, vol. l page .214. 

1. A POLYMERIZABLE COMPOSITION COMPRISING A MIXTURE OF, BY WEIGHT, A MINOR PROPORTION OF (1) A PRIMARY ISOCYANATE REPRESENTED BY THE GENERAL FORMULA CH2=CR-(A)N-CH2-NCO WHERE R REPRESENTS A MEMBER OF THE CLASS CONSISTING OF HYDROGEN AND THE METHYL RADICAL, A REPRESENTS A MEMBER OF THE CLASS CONSISTING OF DIVALENT SATURATED ALIPHATIC HYDROCARBON RADICALS, DIVALENT AROMATIC HYDROCARBON RADICALS, DIVALENT SATURATED ALIPHATIC-SUBSTITUTED AROMATIC HYDROCARBON RADICALS AND DIVALENT AROMATIC-SUBSTITUTED SATURATED ALIPHATIC HYDROCARBON RADICALS, AND N REPRESENTS A VALUE SELECTED FROM THE CLASS CONSISTING OF 0 AND 1, THE METHYLENE RADICAL ATTACHED TO THE ISOCYANATE GROUPING BEING ATTACHED DIRECTLY, WHEN N IS 1, TO ANY CARBON ATOM OF THE DIVALENT RADICAL REPRESENTED BY A, AND A MAJOR PROPORTION OF (2) A DIFFERENT ORGANIC COMPOUND WHICH IS COPOLYMERIZABLE WITH THE ISOCYANATE OF (1), WHICH CONTAINS A SINGLE 